Oxidation dye composition comprising a polycondensate of ethylene oxide and of propylene oxide, and a non-oxyalkylenated glycerolated nonionic surfactant

ABSTRACT

The present invention relates to a dye composition comprising at least one oxidation dye precursor; at least one polycondensate of ethylene oxide and of propylene oxide having the structure (A) below: 
       H—(O—CH 2 —CH 2 ) a —(O—CH(CH 3 )—CH 2 ) b —(O—CH 2 —CH 2 ) a′ —OH  (A),
 
     in which a and a′ range from 2 to 150 and b ranges from 1 to 100, and at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant; the non-oxyalkylenated mono- or polyglycerolated nonionic surfactant(s)/polycondensate(s) of formula (A) weight ratio being between 1 and 20. 
     The invention also relates to a dyeing process using this composition (free of oxidizing agent) after mixing with a composition comprising an oxidizing agent. 
     Another subject of the invention is a two-compartment device, the first compartment comprising the composition according to the invention, free of oxidizing agent, and the second compartment containing a composition comprising at least one oxidizing agent.

The present invention relates to a composition for dyeing human keratin fibres, especially the hair. The invention also relates to a dyeing process using this composition, and to a multi-compartment device containing it.

Among the methods for dyeing human keratin fibres, such as the hair, mention may be made of oxidation dyeing or permanent dyeing. More particularly, this dyeing method uses one or more oxidation dye precursors, and usually one or more oxidation bases optionally combined with one or more couplers.

In general, oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds which, when combined with oxidizing products, can give access to coloured species.

The shades obtained with these oxidation bases are often varied by combining them with one or more couplers, these couplers being chosen especially from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds.

The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.

It is also possible to add to these compositions direct dyes, which are coloured and colouring molecules that have affinity for fibres. The direct dyes generally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine and triarylmethane direct dyes. The presence of such compounds enables the obtained coloration to be further enriched with tints or enables the chromaticity of the obtained coloration to be increased.

Oxidation dyeing processes thus consist in using with these dye compositions a composition comprising at least one oxidizing agent, generally hydrogen peroxide, under alkaline pH conditions in the vast majority of cases. The role of this oxidizing agent is to reveal the coloration, via an oxidative condensation reaction between the oxidation dyes.

The oxidation dye must moreover satisfy a certain number of requirements. Thus, it must be free of toxicological drawbacks, it must enable shades to be obtained in the desired intensity and it must show the resistance to external attacking factors such as light, bad weather, washing, permanent waving, or aspiration and rubbing.

The dyes must also be able to cover grey hair and, finally, they must be as unselective as possible, i.e. they must produce the smallest possible colour differences along the same keratin fibre, which generally comprises areas that are differently sensitized (i.e. damaged) from its end to its root.

It is common practice to use dye compositions containing particular polymers and surfactant systems directed towards the stability of the composition and to maintenance of its viscosity, in order to keep the dye composition on the hair during the time of reaction/penetration of the dyes into the keratin fibre and to limit the risks of running onto the face.

It has moreover been recommended to use surfactants, in particular nonionic surfactants, in oxidation dyeing and especially in dyeing products that are in the form of liquids containing oxidation dye precursors to be mixed with oxidizing compositions, liquid compositions in which the proportions of these surfactants are often large. To obtain satisfactory application conditions after mixing these liquid compositions with the oxidizing compositions, especially with a viscosity that is sufficient to prevent running, it most often proves necessary to thicken slightly the said liquid compositions. Unfortunately, the majority of the thickening polymers lead to rapid demixing of the composition. Moreover, very often, the viscosity-increasing power of the polymers is very greatly reduced when they are combined with relatively large amounts of surfactants.

One of the aims of the present invention is thus to obtain a composition for dyeing the hair, which is stable over time and which remains localized on the hair during application without running, while at the same time conserving the dyeing properties obtained on the hair, in particular conserving powerful, chromatic and uniform colorations between the end and the root of the same fibre and from one fibre to another.

This aim is achieved by the present invention, one subject of which is a dye composition comprising at least one oxidation dye precursor, at least one polycondensate of ethylene oxide and of propylene oxide having the chemical formula (A) below:

H—(O—CH₂—CH₂)_(a)—(O—CH(CH₃)—CH₂)_(b)—(O—CH₂—CH₂)_(a′)—OH  (A)

in which a and a′ range from 2 to 150 and b ranges from 1 to 100, and at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant; the non-oxyalkylenated mono- or polyglycerolated nonionic surfactant(s)/polycondensate(s) of formula (A) weight ratio ranging from 1 to 20.

The invention also relates to a hair dyeing process that consists in applying to the fibres the composition of the invention, in the presence of an oxidizing agent.

A subject of the invention is also a two-compartment device containing, in one of the compartments, the composition of the invention as defined above (free of oxidizing agent) and, in the other compartment, a composition comprising at least one oxidizing agent.

Thus, the invention makes it possible to obtain a thickened composition that is stable over time, which remains in place after application on the hair, without the risk of running. In addition, this composition has improved dyeing properties.

In the description, the term “at least one” is equivalent to “one or more”.

Unless otherwise indicated, the limits of a range of values are included within that range.

As indicated previously, the composition according to the invention comprises at least one polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensate.

Advantageously, the polycondensate of ethylene oxide and of propylene oxide of formula (A) corresponds to a polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensate.

Preferably, in the chemical structure (A) described above, a and a′ range from 10 to 130 and b ranges from 20 to 80. In accordance with an even more particular embodiment, a and a′ range from 50 to 130 and b ranges from 30 to 80, and preferably a and a′ range from 80 to 130 and b ranges from 40 to 80. According to one particular embodiment, a and a′ are identical.

The polycondensate of ethylene oxide and of propylene oxide that is useful in the composition of the invention preferably has a weight-average molecular weight ranging from 250 to 19 000, better still ranging from 1200 to 15 000, in particular ranging from 1500 to 10 000 and even better still ranging from 1500 to 5000.

Advantageously, the said polycondensate of ethylene oxide and of propylene oxide has a cloud point, at 10 g/l in distilled water, of greater than or equal to 20° C. and preferably of greater than or equal to 60° C. The cloud point is measured according to the standard ISO 1065.

As polycondensates of ethylene oxide and of propylene oxide that may be used according to the invention, mention may be made of the polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates sold under the name Synperonic, for instance Synperonic® PE/F32 (INCI name: Poloxamer 108), Synperonic® PE/F108 (INCI name: Poloxamer 338), Synperonic® PE/L44 (INCI name: Poloxamer 124), Synperonic® PE/L42 (INCI name: Poloxamer 122), Synperonic® PE/F127 (INCI name: Poloxamer 407), Synperonic® PE/F88 (INCI name: Poloxamer 238), Synperonic® PE/L64 (INCI name: Poloxamer 184), Synperonic® PE/F88 (INCI name: Poloxamer 238), Synperonic® PE/F87 (INCI name: Poloxamer 237) from the company Croda, or Lutrol® F68 (INCI name: Poloxamer 188) by the company BASF.

According to one embodiment of the invention, the amount of polycondensate of ethylene oxide and propylene oxide preferably ranges from 0.1% to 20% by weight, even more preferentially from 0.5% to 10% by weight and better still from 1% to 5% by weight relative to the total weight of the composition.

The oxidation dyes that are useful in the composition of the invention are generally chosen from oxidation bases and couplers.

By way of example, the oxidation bases are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof.

Among the para-phenylenediamines that may be mentioned, for example, are para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine, N-(4′-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-n-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4′-aminophenyl)pyrrolidine, and the addition salts thereof with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and 2-β-acetylaminoethyloxy-para-phenylenediamine, and the addition salts thereof with an acid, are particularly preferred.

Among the bis(phenyl)alkylenediamines that may be mentioned, for example, are N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine, N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(4-methylaminophenyl)tetramethylenediamine, N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the addition salts thereof.

Among the para-aminophenols that may be mentioned, for example, are para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.

Among the ortho-aminophenols that may be mentioned, for example, are 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the addition salts thereof.

Among the heterocyclic bases that may be mentioned, for example, are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, for instance 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and the addition salts thereof.

Other pyridine oxidation bases that are useful in the present invention are the 3-aminopyrazolo[1,5-a]pyridine oxidation bases or the addition salts thereof described, for example, in patent application FR 2 801 308. Examples that may be mentioned include pyrazolo[1,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine, 2-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyrid-3-ylamine, (3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine, pyrazolo[1,5-a]pyridine-3,7-diamine, 7-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine, pyrazolo[1,5-a]pyridine-3,5-diamine, 5-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol, 3-aminopyrazolo[1,5-a]pyridin-6-ol and 3-aminopyrazolo[1,5-a]pyridin-7-ol, and the addition salts thereof.

Among the pyrimidine derivatives that may be mentioned are the compounds described, for example, in the patents DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96/15765, such as 2,4,5,6-tetraminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and their tautomeric forms, when a tautomeric equilibrium exists.

Among the pyrazole derivatives that may be mentioned are the compounds described in the patents DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl-pyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and the addition salts thereof. 4,5-Diamino-1-(β-methoxyethyl)pyrazole may also be used. A 4,5-diaminopyrazole will preferably be used, and even more preferentially 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or a salt thereof.

Pyrazole derivatives that may also be mentioned include diamino-N,N-dihydro-pyrazolopyrazolones and especially those described in patent application FR-A-2 886 136, such as the following compounds and the addition salts thereof: 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-di-(2-hydroxyethyl)-1,2-dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one, 4-amino-1,2-diethyl-5-(pyrrolidin-1-yl)-1,2-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one. 2,3-Diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a salt thereof will preferably be used.

4,5-Diamino-1-(β-hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a salt thereof will preferentially be used as heterocyclic bases.

Among these useful couplers, mention may be made especially of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof.

Mention may be made, for example, of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)-benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylamino-benzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxy-pyridine, 1-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(β-hydroxy-ethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole and 6-methylpyrazolo[1,5-a]benzimidazole, the addition salts thereof with an acid, and mixtures thereof.

In general, the addition salts of the oxidation bases and couplers that may be used in the context of the invention are especially selected from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

According to one embodiment, the composition comprises at least one oxidation base and optionally a coupler.

The oxidation base(s) each advantageously represent from 0.0001% to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition.

The content of coupler(s), if it is (they are) present, each advantageously represent from 0.0001% to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition.

The composition of the invention also comprises at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant. The term “oxyalkylenated” refers to a divalent radical —R′—O— in which R′ represents a linear C₁-C₄ or branched C₃-C₄ alkylene radical.

In particular, the non-oxyalkylenated mono- or polyglycerolated nonionic surfactants are chosen from the group formed by mono- or polyglycerolated fatty alcohols.

The term “fatty alcohol” more particularly denotes aliphatic alcohols comprising a saturated alkyl chain or an alkenyl chain comprising at least one unsaturation (—C═C—) and preferably from 1 to 3 unsaturations, these chains being linear or branched and comprising from 8 to 40 carbon atoms and more preferentially from 10 to 30 carbon atoms. The alkyl or alkenyl chain may optionally be substituted with one or more additional hydroxyl groups.

More specifically, the fatty alcohols are preferably of formula R—OH, with R denoting a linear or branched alkyl or alkenyl radical, optionally substituted with a hydroxyl group and comprising from 8 to 40 carbon atoms and more preferentially from 10 to 30 carbon atoms.

The non-oxyalkylenated glycerolated nonionic surfactant(s) preferably correspond to formula (I) below:

in which:

R represents a linear or branched alkyl or alkenyl radical comprising 1 to 3 unsaturations (—C═C—), comprising from 8 to 40 carbon atoms and preferably from 10 to 30 carbon atoms;

m represents an average number ranging from 1 to 30, preferably from 1 to 15 and even more preferentially from 1.5 to 10.

Preferably, the non-oxyalkylenated mono- or polyglycerolated nonionic surfactants of formula (I) are chosen from C₁₂-C₂₄ fatty alcohols comprising from 1 to 10 mol of glycerol, more particularly oleyl alcohol containing 2 mol of glycerol, oleyl alcohol containing 4 mol of glycerol, lauryl alcohol containing 1.5 mol of glycerol and dodecanediol containing 3.5 mol of glycerol (polyglyceryl-3 hydroxylauryl ether).

The non-oxyalkylenated mono- or polyglycerolated nonionic surfactants are advantageously present in concentrations ranging from 0.1% to 40% by weight, preferably from 0.5% to 25% by weight, more particularly from 0.5% to 15% by weight and preferably from 1% to 10% by weight relative to the total weight of the composition.

Preferably, the non-oxyalkylenated glycerolated nonionic surfactant(s)/polycondensate(s) of formula (A) weight ratio ranges from 1.25 to 10, more particularly from 1.25 to 5 and preferably from 3 to 4.

The composition according to the invention may optionally comprise synthetic or natural direct dyes, chosen from ionic or nonionic species, preferably cationic or nonionic species.

Examples of suitable direct dyes that may be mentioned include azo dyes; methine dyes; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanin dyes, and natural direct dyes, alone or as mixtures.

Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Extracts or decoctions containing these natural dyes and in particular henna-based poultices or extracts, may also be used.

When they are present, the direct dye(s) more particularly represent from 0.0001% to 10% by weight and preferably from 0.005% to 5% by weight of the total weight of the composition.

The medium that is suitable for dyeing, also known as the dye support, generally comprises water or a mixture of water and of one or more organic solvents, for example C₁-C₄ lower alkanols such as ethanol and isopropanol, polyols, for instance propylene glycol, dipropylene glycol or glycerol, and polyols, for instance dipropylene glycol monomethyl ether.

According to one particular embodiment, the composition of the invention comprises a C₁-C₄ aliphatic alcohol, especially ethanol or isopropanol.

These solvents are generally present in proportions that may be between 1% and 40% by weight and even more preferentially between 3% and 30% by weight relative to the total weight of the dye composition.

The dye composition in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic (other than those that are useful in the invention), amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral thickeners such as silicates or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersants, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones, film-forming agents, ceramides, preserving agents and opacifiers.

The above adjuvants are generally present in an amount, for each of them, of between 0.01% and 20% by weight relative to the weight of the composition.

Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s) such that the advantageous properties intrinsically associated with the oxidation dye composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).

The pH of the dye composition in accordance with the invention is generally between 5 and 14 approximately and preferably greater than 5.

According to one particular embodiment, the pH is between 6 and 11.

It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres, or alternatively using standard buffer systems.

Among the acidifying agents that may be mentioned, for example, are mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.

Mention may be made, among the basifying agents, by way of example, of aqueous ammonia, alkaline carbonates, alkanolamines, such as mono-, di- and triethanolamines, and their derivatives, sodium hydroxide, potassium hydroxide and the compounds with the following formula:

in which W is a propylene residue optionally substituted with a hydroxyl group or a C₁-C₄ alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom or a C₁-C₄ alkyl or C₁-C₄ hydroxyalkyl radical.

Advantageously, the composition according to the invention has a content of basifying agent(s) ranging from 0.01% to 30% by weight and preferably from 0.1% to 20% by weight relative to the weight of the composition.

According to one embodiment, the composition comprises at least one alkaline agent.

The composition according to the invention may comprise one or more oxidizing agents. Conventionally, the oxidizing agent is added to the composition at the time of use.

More particularly, the oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, for instance alkali metal or alkaline-earth metal persulfates, perborates and percarbonates, and also peracids and precursors thereof.

Advantageously, the oxidizing agent is hydrogen peroxide. The content of oxidizing agent(s) more particularly represents from 0.1% to 20% by weight and preferably from 0.5% to 10% by weight relative to the weight of the composition.

Preferably, the oxidizing agent is hydrogen peroxide in aqueous solution, the concentration of which ranges, more particularly, from 0.1% to 50% by weight, more particularly between 0.5% and 20% by weight and even more preferentially between 1% and 15% by weight relative to the weight of the oxidizing composition.

Preferably, the composition of the invention before mixing with the oxidizing agent is in liquid form at a temperature of 25° C. and at atmospheric pressure (760 mmHg), i.e. it is capable of flowing under the action of its own weight.

Preferably, the viscosity at a temperature of 25° C. and at a shear rate of 1 s⁻¹ of the composition of the invention before mixing with the oxidizing agent is between 10⁻² Pa·s and 5 Pa·s and preferably between 10⁻¹ Pa·s and 2 Pa·s. It may be measured using a Thermo Haake RS600 rheometer with cone-plate geometry or an equivalent machine.

Preferably, the composition of the invention before mixing with the oxidizing agent contains a total amount of ionic or nonionic surfactants of greater than 8% and even more preferentially greater than 10%.

The dyeing process according to the invention thus consists in mixing a composition (free of oxidizing agent) comprising at least one dye precursor, at least one polycondensate of polyethylene and of polypropylene as defined previously, and at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant; the non-oxyalkylenated mono- or polyglycerolated nonionic surfactant(s)/polycondensate(s) of formula (A) weight ratio ranging from 1 to 20, with a composition comprising an oxidizing agent, and in applying this composition to wet or dry human keratin fibres.

The composition is then left in place for a time usually ranging from one minute to one hour and preferably from 5 minutes to 30 minutes.

The temperature during the process is conventionally between room temperature (between 15 and 25° C.) and 80° C. and preferably between room temperature and 60° C.

After the treatment, the human keratin fibres are optionally rinsed with water, optionally washed with a shampoo and then rinsed with water, before being dried or left to dry.

EXAMPLES

The following compositions were prepared:

% by weight Composition A (AM) 1,4-Diaminobenzene 0.36 2-Methyl-1,3-dihydroxybenzene 0.15 1,3-Dihydroxybenzene 0.77 6-Hydroxyindole 0.07 1-Hydroxy-3-aminobenzene 0.41 Rapeseed fatty acid amide 4 OE (PEG-4 rapeseed amide) 8.12 Decyl alcohol 3 OE (Deceth-3) 6.93 Monoglycerolated lauryl alcohol (glyceryl lauryl ether) 7 Oleyl alcohol 1.1 Laureth-5 carboxylic acid 4.5 Ethanolamine 3.66 EDTA 0.2 Ethanol 8.2 Propylene glycol 6.2 Hexylene glycol 3 Dipropylene glycol 3 POE/POP/POE (Poloxamer 338 sold by BASF; a = a′ = 128 2 b = 54) Polyquaternium-6 1.36 Ammonium thiolactate 0.464 Erythorbic acid 0.12 Ammonium hydroxide 2.88 Water qs 100 Glyceryl lauryl ether/Poloxamer 338 weight ratio 3.5 (AM): Active Material

% by weight Composition B (AM) 1,4-Diaminobenzene 0.36 2-Methyl-1,3-dihydroxybenzene 0.15 1,3-Dihydroxybenzene 0.77 6-Hydroxyindole 0.07 1-Hydroxy-3-aminobenzene 0.41 Rapeseed fatty acid amide 4 OE (PEG-4 rapeseed amide) 8.12 Decyl alcohol 3 OE (Deceth-3) 6.93 Monoglycerolated lauryl alcohol (glyceryl lauryl ether) 7 Oleyl alcohol 1.1 Laureth-5 carboxylic acid 4.5 Ethanolamine 5.66 EDTA 0.2 Ethanol 8.2 Propylene glycol 6.2 Hexylene glycol 3 Dipropylene glycol 3 POE/POP/POE (Poloxamer 338 sold by BASF; a = a′ = 128 2 b = 54) Polyquaternium-6 1.36 Thiolactic acid 0.251 Erythorbic acid 0.12 Water qs 100 Glyceryl lauryl ether/Poloxamer 338 weight ratio 3.5 (AM): Active Material

% by weight Composition C (AM) 1,4-Diaminobenzene 0.36 2-Methyl-1,3-dihydroxybenzene 0.15 1,3-Dihydroxybenzene 0.77 6-Hydroxyindole 0.07 1-Hydroxy-3-aminobenzene 0.41 Rapeseed fatty acid amide 4 OE (PEG-4 rapeseed amide) 8.12 Decyl alcohol 3 OE (Deceth-3) 6.93 Monoglycerolated lauryl alcohol (glyceryl lauryl ether) 7 Oleyl alcohol 1.1 Laureth-5 carboxylic acid 4.5 Ethanolamine 5.66 EDTA 0.2 Ethanol 8.2 Propylene glycol 6.2 Hexylene glycol 6 POE/POP/POE (Poloxamer 338 sold by BASF; a = a′ = 128 2 b = 54) Polyquaternium-6 1.36 Thiolactic acid 0.251 Erythorbic acid 0.12 Water qs 100 Glyceryl lauryl ether/Poloxamer 338 weight ratio 3.5 (AM): Active material

Compositions A, B and C are stable over time.

Each of them is mixed with 1.5 times its own weight of an oxidizing composition comprising 7.5% hydrogen peroxide at pH 2.

The mixtures obtained apply easily to dark chestnut-brown hair, without running.

After a leave-on time of 30 minutes at 25° C. followed by rinsing, the hair is washed and dried.

The hair is then uniformly dyed in a strong golden light chestnut-brown colour with the two mixtures obtained from compositions A, B and C. 

1-15. (canceled)
 16. A dye composition comprising: at least one oxidation dye precursor; at least one polycondensate of ethylene oxide and of propylene oxide of Formula (A): H—(O—CH₂—CH₂)_(a)—(O—CH(CH₃)—CH₂)_(b)—(O—CH₂—CH₂)_(a′)—OH  (A) wherein a and a′ range from 2 to 150 and b ranges from 1 to 100; and at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant, wherein the weight ratio of the at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant to the at least one polycondensate of ethylene oxide and of propylene oxide ranges from about 1 to about
 20. 17. The dye composition according to claim 16, wherein the at least one oxidation dye precursor is at least one oxidation base chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and the addition salts thereof, and optionally at least one coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers, heterocyclic couplers, and the addition salts thereof.
 18. The dye composition according to claim 16, wherein for the at least one polycondensate of ethylene oxide and of propylene oxide, a and a′ range from 10 to 130 and b ranges from 20 to
 80. 19. The dye composition according to claim 16, wherein for the at least one polycondensate of ethylene oxide and of propylene oxide, a and a′ range from 80 to 130 and b ranges from 40 to
 80. 20. The dye composition according to claim 16, wherein for the at least one polycondensate of ethylene oxide and of propylene oxide, a and a′ are identical.
 21. The dye composition according to claim 16, wherein the weight ratio of the at least one non-oxyalkylenated mono- or polyglycerolated surfactant to the at least one polycondensate of ethylene oxide and of propylene oxide ranges from about 1.25 to about
 10. 22. The dye composition according to claim 16, wherein the weight ratio of the at least one non-oxyalkylenated mono- or polyglycerolated surfactant to the at least one polycondensate of ethylene oxide and of propylene oxide ranges from about 3 to about
 4. 23. The dye composition according to claim 16, wherein the amount of the at least one polycondensate of ethylene oxide and of propylene oxide ranges from about 0.1% to about 20% by weight, relative to the total weight of the composition.
 24. The dye composition according to claim 16, wherein the amount of the at least one polycondensate of ethylene oxide and of propylene oxide ranges from about 1% to about 5% by weight, relative to the total weight of the composition.
 25. The dye composition according to claim 16, wherein the at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant is chosen from non-oxyalkylenated mono- and polyglycerolated fatty alcohols.
 26. The dye composition according to claim 16, in which the at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant corresponds to formula (I):

wherein: R is chosen from linear and branched alkyl and alkenyl radicals comprising 1 to 3 unsaturations and comprising from 8 to 40 carbon atoms; and m is average number ranging from 1 to
 30. 27. The dye composition according to claim 16, wherein the at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant is chosen from C₁₂-C₂₄ fatty alcohols comprising from about 1 to about 10 mol of glycerol.
 28. The dye composition according to claim 27, wherein the C₁₂-C₂₄ fatty alcohols are chosen from oleyl alcohol comprising about 4 mol of glycerol, lauryl alcohol comprising about 1.5 mol of glycerol, and dodecanediol comprising about 3.5 mol of glycerol.
 29. The dye composition according to claim 16, wherein the at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant represents from about 0.1% to about 40% by weight.
 30. The dye composition according to claim 16, wherein the at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant represents from about 1% to about 10% by weight.
 31. The dye composition according to claim 16, wherein the dye composition is liquid at about 25° C. and at atmospheric pressure (760 mmHg).
 32. The dye composition according to claim 16, comprising a total amount of ionic or nonionic surfactants of greater than about 8%.
 33. The dye composition according to claim 16, further comprising at least one oxidizing agent.
 34. A process for dyeing hair, comprising: mixing at least one oxidizing agent and a composition comprising at least one oxidation dye precursor, at least one polycondensate of ethylene oxide and of propylene oxide of Formula (A): H—(O—CH₂—CH₂)_(a)—(O—CH(CH₃)—CH₂)_(b)—(O—CH₂—CH₂)_(a′)—OH  (A) wherein a and a′ range from 2 to 150 and b ranges from 1 to 100, and at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant, wherein the weight ratio of the at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant to the at least one polycondensate of ethylene oxide and of propylene oxide ranges from about 1 to about 20; and applying the resultant mixture to hair.
 35. A two-compartment device comprising: in a first compartment, a first composition comprising: at least one oxidation dye precursor, at least one polycondensate of ethylene oxide and of propylene oxide of Formula (A): H—(O—CH₂—CH₂)_(a)—(O—CH(CH₃)—CH₂)_(b)—(O—CH₂—CH₂)_(a′)—OH  (A) wherein a and a′ range from 2 to 150 and b ranges from 1 to 100, and at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant, wherein the weight ratio of the at least one non-oxyalkylenated mono- or polyglycerolated nonionic surfactant to the at least one polycondensate of ethylene oxide and of propylene oxide ranges from about 1 to about 20; and in a second compartment, a second composition comprising at least one oxidizing agent. 